CN105555424A - Thin film production method and transparent conductive film - Google Patents
Thin film production method and transparent conductive film Download PDFInfo
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- CN105555424A CN105555424A CN201480052051.7A CN201480052051A CN105555424A CN 105555424 A CN105555424 A CN 105555424A CN 201480052051 A CN201480052051 A CN 201480052051A CN 105555424 A CN105555424 A CN 105555424A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Human Computer Interaction (AREA)
- General Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Conductive Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The purpose of the present invention is to provide, as a technique for obtaining a thin film, a new method to take the place of conventional techniques. This thin film production method is characterized by including the following: a misting step for misting a dispersion solution containing fine particles; a supply step for supplying the misted dispersion solution to a substrate; and a drying step for drying the dispersion fluid that was supplied onto the substrate.
Description
Technical field
The present invention relates to formation method, the nesa coating of film.The priority of the application number 2013-225549 of the Japan Patent of application claims application on October 30th, 2013, for the designated state that enroll of accreditation based on document reference pattern, enrolls the content described in this application in the application by referring to mode.
Background technology
The nesa coating be made up of tin indium oxide (ITO), zinc oxide (ZnO) etc. is widely used as the transparency electrode of liquid crystal display, solar cell.These nesa coatings utilize sputtering method to generate usually.
In addition, as the method beyond sputtering method, such as Patent Document 1 discloses the film forming utilizing the film formation device of metal oxide film to carry out metal oxide film, " feature of this film formation device is, it possesses the first container (5A) adding the material solution (10) had containing metal, add the second container (5B having hydrogen peroxide, 18), placement substrate (2) and there is the reaction vessel (1) of the heater (3) heating described substrate, connect described first container and described reaction vessel, by first path (L1) of described material solution from described first supply for receptacles to described reaction vessel, connect described second container and described reaction vessel, described hydrogen peroxide is supplied to second path (L2) of described reaction vessel from described second container ".In the film formation device recorded in patent document 1, make the material solution containing metal and hydrogen peroxide substrate after the heating reacts, carry out the film forming of metal oxide film.
Prior art document
Patent document
Patent document 1: No. 2011/151889th, International Publication
Summary of the invention
The problem that invention will solve
The object of the invention is to provide a kind of new method of above-mentioned prior art that replaces as the technology obtaining film.
For solving the means of problem
Mode of the present invention completes to achieve these goals, and the feature of the manufacture method of film of the present invention is, it has the atomization procedure made containing fine-grained dispersion liquid atomization; Dispersion liquid through atomization is supplied to the supply step of substrate; Make the drying process of the described dispersion liquid drying be supplied on described substrate.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, the particle diameter of described particulate contained in the dispersion liquid of atomization is below 100nm.
In addition, feature is also that the described substrate in the manufacture method of the film of mode of the present invention contains resin, has pliability.
In addition, feature is also that the described drying process in the manufacture method of the film of mode of the present invention carries out at the temperature of the softening point lower than described substrate.
In addition, feature is also that described drying process in the manufacture method of the film of mode of the present invention carries out at the temperature of less than 40 DEG C more than 10 DEG C.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, it possesses to be formed on the substrate scolds water patterns formation process by hydrophilic portion and the parent of the pattern of scolding water portion to form, and scolds water patterns formation process to be formed with described parent scold the substrate of water patterns to carry out described supply step to utilizing described parent.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, after described drying process, possess the Ultraviolet radiation operation to described substrate irradiation ultraviolet radiation, again supply step is carried out to the described substrate through described Ultraviolet radiation operation irradiation ultraviolet radiation.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, in described supply step, described particulate contained in the described mist of supply before described Ultraviolet radiation operation is different from described particulate contained in the described mist supplied after described Ultraviolet radiation operation.
In addition, feature is also that ultraviolet that the described Ultraviolet radiation operation in the manufacture method of the film of mode of the present invention is irradiated at least comprises the wavelength of below 200nm.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, in described supply step, described substrate is inclined relative to horizontal.
In addition, the feature of the manufacture method of the film of mode of the present invention is also, in described supply step, described substrate is relative to the face tilt orthogonal with the described direction of the supply.
In addition, feature is also that the described particulate in the manufacture method of the film of mode of the present invention is the metal oxide microparticle of any one containing indium, zinc, tin and titanium.
In addition, the feature of the nesa coating of mode of the present invention is, it is obtained by the manufacture method of above-mentioned film.Invention effect
The present invention can provide a kind of new method of prior art that replaces as the technology obtaining film.
Accompanying drawing explanation
Fig. 1 is the sectional view of an example of the film build method of metal oxide film for illustration of present embodiment.
Fig. 2 is the figure of an example of the film formation device illustrated in present embodiment.
Fig. 3 is the sectional view (its 1) of an example of the manufacture method of conducting film for illustration of this variation.
Fig. 4 is the sectional view (its 2) of an example of the manufacture method of conducting film for illustration of this variation.
Fig. 5 is for illustrating the figure of the summary of RolltoRoll (volume to volume) mode manufacturing installation.
Fig. 6 is the figure of the sheet resistance that different heating baking temperature is shown.
Fig. 7 is the SEM image of the ito film obtained.
Fig. 8 is the figure of the sheet resistance of the different heating baking temperature that the metal oxide film obtained is shown.
Fig. 9 is the surface observation result based on SEM image.
Figure 10 illustrates the sheet resistance value of GZO film and the figure of visible light transmissivity that obtain.
Figure 11 is the SEM image of the GZO film obtained.
Figure 12 illustrates the GZO film that the obtains figure based on the analysis result of EDX.
Figure 13 is the SEM image of the film GZO film obtained.
Figure 14 is the figure of the relation of substrate temperature when film forming is shown and sheet resistance.
Figure 15 is the SEM image of the ito film of scolding on water patterns substrate.
Figure 16 is the SEM image of the GZO film of scolding on water patterns substrate.
Figure 17 is the SEM image of the substrate being heated to 60 DEG C.
Figure 18 is the SEM image of the substrate being heated to 80 DEG C.
Figure 19 is the SEM image of the ito film obtained.
Detailed description of the invention
Below, with reference to accompanying drawing, the example for embodiment of the present invention is described.
Fig. 1 is the sectional view of an example of the formation method of film for illustration of present embodiment.
(the 1st operation)
First, prepared substrate 10.Substrate 10 can use usually baseplate material used.Such as glass, PET (PET), PEN (PEN), polyether sulfone (PES), PEI, polyether-ether-ketone, polyphenylene sulfide, polyarylate, polyimides, Merlon (PC), cellulose triacetate (TAC), cellulose-acetate propionate (CAP) etc. can be used.
Further, as required substrate 10 is cleaned.For cleaning method, the conventional methods such as Ultrasonic Cleaning can be used.Afterwards, UV (ultraviolet: ultraviolet) is irradiated for substrate 10.For the irradiation of UV, use conventional UV irradiation unit, expect the ultraviolet irradiating below 200nm (such as 10nm ~ 200nm) wavelength.By irradiating UV, remove the impurity on substrate 10 surface, thus can hydrophiling.
(the 2nd operation)
Then, for substrate 10, spray by the mist formed containing fine-grained dispersion liquid, carry out the film forming of metal oxide film 2.
Fig. 2 is the figure of an example of the film formation device illustrated in present embodiment.Film formation device has generation containing the 1st groove of fine-grained mist, as making the 2nd groove of the mist collector of mist homogenising, substrate 10 being carried out to the 3rd groove of the spraying of mist.
Contain material solution 5 in 1st groove, this material solution 5 is the dispersion liquid of microparticulate in dispersant.Particulate can use indium, zinc, tin or titanium etc. to have the metal particle of electric conductivity, contain the metal oxide microparticle of wherein at least one.They can be used alone, and also can be combined two or more and use.The nanoparticle of particulate to be particle diameter be 1 ~ 100nm.It should be noted that, as particle diameter, the major axis of the particulate such as obtained according to SEM image and the mean value of minor axis can be used.It should be noted that, in the present embodiment, be described as the mode of particulate to use metal oxide microparticle.
As long as dispersant can disperse particles, alcohol and their mixtures such as water, isopropyl alcohol (IPA), ethanol can be used.It should be noted that, in the 1st groove, flow into air 22, for the formation of the stream of mist.
In addition, ultrasonic oscillator 21 is contained in the 1st groove.Utilize this ultrasonic oscillator 21, the dispersion liquid containing metal oxide microparticle is atomized.The particle diameter of mist expects to be less than 10 μm (such as 1 ~ 10 μm).The mist generated in the 1st groove, via the pipe being arranged on the 1st groove, transports to the 2nd groove.In the 2nd groove, excessive mist accumulates in the bottom of groove, and the mist of uniform particle sizes, via the pipe being arranged on the 2nd groove, transports to the 3rd groove.For from the 2nd groove to the 3rd groove, expect the mist of the particle diameter being configured to conveyance less than 5 μm (such as 1 ~ 5 μm).
In the 3rd groove, placement substrate 10, is sprayed to substrate from the mist of the 2nd groove conveyance.In the 3rd groove, with the stipulated time substrate 10 carried out to the spraying of mist.Further, by being attached to the dispersant vaporization of the mist of substrate 10, thus metal oxide film is formed on substrate 10 surface.It should be noted that, after spraying after certain hour, before mist is vaporized, on the substrate 10, the dispersion liquid of droplet treatment flows down thus, cannot form uniform metal oxide film on the substrate 10 in new mist attachment.Stop the time of the spraying of mist for the moment that liquefaction occurs the mist containing metal oxide microparticle and flow down from substrate 10, also can be the moment of the metal oxide film forming desired thickness on the substrate 10 for substrate 10.
In the 3rd groove, during superheated substrate 10, substrate 10 is likely out of shape owing to softening.Therefore, in the 3rd groove, carry out the spraying of mist under being desirably in the temperature lower than the softening point of substrate, form metal oxide film.In addition, during the spraying of mist, when being heated to more than set point of temperature by substrate 10, be attached to the metal oxide microparticle aggegation of substrate 10, the metal oxide film of formation has high resistance.Therefore, carry out the spraying of mist under expecting to be configured to the temperature of below 40 DEG C (such as 10 DEG C ~ 40 DEG C) further, form metal oxide film.
It should be noted that, herein, softening point refers to: during heated substrates, and substrate softens, and starts the temperature producing distortion.It can utilize such as obtains according to the test method of JISK7207 (A method).
Detailed content will, in description, when formation metal oxide film selective for substrate 10, by scolding moisture film for the selective formation of substrate 10 in advance, make mist be attached to hydrophilic portion.Now, if substrate 10 horizontal arrangement, be then attached to and scold the dispersion liquid in water portion not scolded water, cannot selective formation metal oxide film.Therefore, in the 3rd groove, expect the spraying substrate 10 be inclined relative to horizontal being carried out to mist.
Similarly, in the 3rd groove, expect the spraying substrate 10 relative to the face tilt orthogonal with the spray direction of mist being carried out to mist.This is in order to the impulse force removal of the spraying with mist is attached to the excessive metal oxide microparticle of scolding water portion.
It should be noted that, film formation device can omit the mist collector of the 2nd groove.In it is possible to the film forming of with easier device, substrate being carried out to metal oxide film.
In addition, for the production method of mist, make except using above-mentioned ultrasonic oscillator 21 except it produces, can also use: to the tubule of spraying droplets directly being applied voltage to produce the electrostatic of mist; The gas and the liquid that increase flow velocity by making applying pressure collide, thus make the adding pressure type that the mist of generation disperses; The dish of High Rotation Speed instils drop, makes the rotating disc type that the mist of generation disperses under centrifugal action; The restricting orifice with micro-scale pores circulates drop, now cutting off drop by utilizing piezoelectric element etc. to apply vibration, producing the throttle orifice oscillatory type etc. of micro-dimension drop thus.For the production method of mist, according to cost, performance etc., suitably select these methods.Two or more methods can certainly be combined to produce mist.
(the 3rd operation)
Return Fig. 1 to be described.Afterwards, for the substrate 10 being formed with metal oxide film 2, carry out heating to make it dry.In the same manner as above-mentioned example, expect that heating-up temperature is now at the temperature of the softening point lower than substrate 10.Heating can be carried out under the low vacuum of about 30Pa, also can carry out under Ar gas atmosphere.For hot situation, according to the situation etc. of film forming, suitably distinguish use.It should be noted that, in this operation, drying is carried out in non-essential utilization heating.Such as at normal temperatures, substrate 10 can be set with the stipulated time, carry out drying thus.
It should be noted that, above-mentioned 1st operation is not necessary operation.It is the operation of carrying out as pre-treatment, in order to make mist adhere on the substrate 10 in the 2nd operation, as long as therefore mist attachment on the substrate 10, does not limit method.
By above process, forming metal oxide film on the substrate 10, as required, by again carrying out the process from the 1st operation to the 3rd operation, the 2nd layer of metal oxide film can be obtained.In this situation, the base-plate cleaning of the 1st operation can be omitted.It should be noted that, by making in the mist of the 1st layer contained metal oxide microparticle be identical material with the metal oxide microparticle of the 2nd layer, the metal oxide film of abundant thickness can be obtained.Or by making the metal oxide film of the 1st layer be different materials from the metal oxide film of the 2nd layer, can according to purposes, object and distinguish use conducting film.
Above, in the present embodiment, in the formation process of film, substrate is not heated when carrying out film forming.Therefore, it is possible to obtain the low metal oxide film of resistance value.In addition, even if for heat labile substrate, also effectively film forming can be carried out.
(variation)
Then, modified embodiment of the present embodiment is described.
Fig. 3 is the sectional view of an example of the manufacture method of conducting film for illustration of this variation.In this variation, the metal oxide film utilizing above-mentioned embodiment to be formed is used to manufacture conducting film.The conducting film manufactured is used for touch pad etc. as static capacity switch.
(the 1st operation)
First, UV is irradiated for substrate 10.UV irradiates the object of carrying out and is to remove the impurity on substrate 10.It should be noted that, the 1st operation can be omitted.
(the 2nd operation)
Then, painting erosion resistant agent 11 on the substrate 10.Resist 11 is the Conventional photosensitive material for photoresist, for coating, can use known coating process, the coating processes such as such as spin-coating method, dip coating, spraying process.
(the 3rd operation)
Then, the selective exposure of substrate 10 is made.Specifically, use the photomask being applied with required pattern in advance, make the selective exposure of a part of the resist 11 on substrate 10.Afterwards, by making substrate 10 develop, the resist 11 being patterned as required form is obtained.It should be noted that, the mode using photomask to cover x direction (left and right directions of Fig. 3) the selective exposure afterwards of substrate 10 is described herein for convenience of description.
(the 4th operation)
Then, moisture film 3 is scolded in formation on the substrate 10.For scolding moisture film 3, use the existing materials such as fluorine system water repellent.Such as scolding moisture film 3,3M can be used
tMn o vec
tMeGC-1720 (Sumitomo 3M Co., Ltd. system).For the film build method of scolding moisture film 3, same with the coating of above-mentioned resist 11, use existing film build method to carry out film forming.
(the 5th operation)
Then, the resist 11 on substrate 10 is peeled off.For the stripping of resist 11, use existing stripper to carry out, such as, use acetone etc. to carry out.By peeling off resist 11, can peel off together with the moisture film of scolding be formed on resist 11.Thereby, it is possible to obtain being formed required pattern scold moisture film 3.
(the 6th operation)
Then, for substrate 10, make the dispersion liquid containing metal oxide microparticle be atomized and spray, carry out the film forming of metal oxide film 2.Specifically, use the film formation device shown in Fig. 2, carry out film forming by the spraying of mist.Selective being formed scolds moisture film 3 on the substrate 10, and the dispersion liquid attachment of therefore liquefying does not form the part of scolding moisture film 3 on the substrate 10, is namely attached to hydrophilic segment, thus selective formation metal oxide film 2.It should be noted that, be attached to for the moment and scold the dispersion liquid of water section from scolding water section to flow down, to be attached to adjacent hydrophilic segment due to the inclination of substrate 10, or flow down from substrate 10, be accumulated in the bottom of the 3rd groove.Afterwards heat drying is carried out to the metal oxide film 2 formed on the substrate 10.
(the 7th operation)
Then, for substrate 10, dielectric film 4 is formed.It should be noted that, before formation dielectric film 4, UV irradiation can be carried out to substrate.This is because pass through scolding moisture film 3 to carry out UV irradiation, repellency reduces, thus contributes to the formation of dielectric film 4.But the situation etc. of the material formation dielectric film 4 using the viscosity such as organic material high, without the need to considering the impact of scolding the repellency of moisture film 3, therefore can not irradiate UV.Consider the material etc. of dielectric film 4, after carrying out UV irradiation as required, form dielectric film 4 on the substrate 10.
Dielectric film 4 is formed in scolds on moisture film 3 and metal oxide film 2.For dielectric film 4, use such as SnO
2deng non-conductive material.For the formation method of dielectric film 4, by using the existing methods such as spin-coating method, stick coating method, dip coating, the material of regulation being coated on whole and carrying out film forming.
Fig. 4 is the sectional view (its 2) of an example of the manufacture method of touch pad for illustration of this variation.
(the 8th operation)
Then, UV is irradiated for substrate 10.Irradiating UV is to easily form the 2nd layer of metal oxide film on dielectric film 4.
(the 9th operation)
Then, for substrate 10, painting erosion resistant agent 11.For the coating of resist 11, carry out with the order same with the 2nd operation.
(the 10th operation)
Then, substrate 10 is carried out selective exposure and developed.In the 3rd operation, the x direction of photomask to substrate 10 is used to shelter rear selectively to expose, but in this operation, for the y direction (direction orthogonal with the left and right directions of Fig. 4) using photomask to cover substrate 10 afterwards selective mode of carrying out exposing be described.For exposure and development, carry out with the order same with the 3rd operation.
(the 11st, 12 operations)
Then, for substrate 10, moisture film 3 is scolded in coating.Afterwards, scold moisture film 3 together with what be formed in resist 11, peel off the resist 11 remaining in substrate 10.11st operation and the 12nd operation are carried out with the order same with the 4th operation and the 5th operation.
(the 13rd operation)
Then, for substrate 10, the 2nd layer of metal oxide film 2 is formed.For the film forming of metal oxide film 2, same with the 6th operation, use the film formation device shown in Fig. 2.Afterwards, drying is carried out to metal oxide film 2.It should be noted that, in detail in this figure, for the 2nd layer, define metal oxide film 2 at the y set direction of substrate 10, therefore, in the record of the sectional view of substrate 10, define the 2nd layer of metal oxide film 2 on the whole at substrate 10.
(the 14th operation)
Then, for substrate 10, dielectric film 4 is formed.Dielectric film 4 is formed in the top of the metal oxide film 2 carrying out film forming in the 13rd operation.For the formation of dielectric film 4, with the film build method same with the 7th operation, same material is used to carry out.
As mentioned above, in the present embodiment, by being formed, there is the metal oxide film of patterned shape, and form the protective layer based on dielectric film in most surface, the touch pad of change according to static capacity and action can be generated.In addition, by the film forming using above-mentioned film formation device to carry out metal oxide film, compared with common metal oxide film, the metal oxide film that resistance value is low, transparency is high can be obtained.
Fig. 5 is the figure of the summary that RolltoRoll mode manufacturing installation is shown.In this manufacturing installation, when the film 20 formed in roll is arranged on one end of device, the film 20 being formed with metal oxide film is discharged from the other end of device.It should be noted that, film 20 is used as the substrate in above-mentioned embodiment, and it contains resin, has pliability.
(operation 1: cleaning)
First, film 20 is cleaned.For cleaning method, use the conventional methods such as Ultrasonic Cleaning.
(operation 2:UV irradiation)
Then, UV is irradiated for film 20.As mentioned above, for the irradiation of UV, use conventional UV irradiation unit, expect the ultraviolet irradiating below 200nm wavelength.
(operation 3: the spraying of mist)
Then, for film 20, the mist produced from the dispersion liquid being dispersed with metal oxide microparticle of spraying.The film formation device used in operation 3 is film formation device illustrated in fig. 2.It should be noted that, as mentioned above, in film formation device, at the temperature of the softening point lower than film 20, carry out the film forming of metal oxide film.By this operation, the film 20 being attached with metal oxide film can be obtained.
(operation 4: heating)
Then, film 20 is heated, make the metal oxide film being attached to film 20 in operation 3 dry.It should be noted that, as mentioned above, for the temperature that the heats softening point lower than film 20.
(operation 5: slow cooling)
Then, film 20 Slow cooling is made.In this operation, cooling device can be used to cool film 20.
(operation 6:UV irradiation)
In this manufacturing installation, the metal oxide film generated carries out the film forming of the 2nd layer of metal oxide film.Therefore, in this operation, UV irradiation is carried out for film 20, remove impurity, and improve hydrophily.It should be noted that, when the film forming of metal oxide film is terminated with 1 layer, omit the operation that this operation is later.
(operation 7: the spraying of mist)
Then, film 20 is carried out to the spraying of mist.In this operation, in the same manner as operation 3, use the film formation device shown in Fig. 2, for film 20, form metal oxide film.By this operation, the 1st layer of metal oxide film formed carries out the film forming of the 2nd layer of metal oxide film in operation 3.
(operation 8: heating)
Then, film 20 is heated, make the metal oxide film being attached to film 20 in operation 8 dry.
(operation 9: slow cooling)
Then, film 20 Slow cooling is made.
As mentioned above, by using RolltoRoll mode manufacturing installation, on the substrate formed in roll, metal oxide film can be formed continuously.In addition, for containing resin, possess flexual substrate, use the temperature lower than softening point, the film forming of the high metal oxide film of performance can be carried out.
Below, embodiment is shown, mode of the present invention is more specifically described.Wherein, the present invention is not limited to these embodiments.
< embodiment 1>
First, the aqueous dispersions (NanoTekSlurry:C.I.KASEI system) containing ITO particulate is prepared.The particle diameter of ITO particulate is 10 ~ 50nm, and average grain diameter is 30nm.Material and the particle diameter of ITO particulate used in other embodiments are below same with the present embodiment.In addition, the concentration of the metal oxide microparticle in dispersion liquid is 15wt.%.The dispersion liquid of preparation is added in the 1st groove of above-mentioned film formation device, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produce mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.It should be noted that, film formation device used in the present embodiment eliminates the 2nd groove as mist collector.Therefore, mist carries out for being sprayed in the 2nd groove of substrate.It should be noted that, use soda lime glass substrate as substrate.
In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt 45 degree orthogonal with the spray direction of mist, the spraying of lasting 5 minutes mists.Now, not heated substrates, at room temperature sprays.
After substrate being carried out to the spraying of mist, use infrared lamp heater, heat with the different mode of 100 DEG C ~ 200 DEG C.Heat the low vacuum of about the 30Pa formed at use vavuum pump or carry out 10 minutes under inert gas (Ar) atmosphere.
Afterwards, UV (254nm, 185nm mix) is irradiated to the surface of the ito film of drying.Continue afterwards, as described above substrate is configured in the 2nd groove of film formation device, at room temperature, continue the spraying of 5 minutes mists.Afterwards, by utilizing infrared lamp heating devices heat as described above 10 minutes, drying substrates is made.
(evaluation)
Fig. 6 is the figure of the sheet resistance that different heating baking temperature is shown.It should be noted that, sheet resistance shown here utilizes four probe method to measure.With reference to known during data shown in Fig. 6, form the heat resisting temperature of film of substrate, namely in the low-temperature region of less than 200 DEG C, obtain the sheet resistance of 100 Ω/sq. units.
In addition, known when studying the low vacuum treatment based on the process in the atmospheric pressure under inert gas (Ar) atmosphere and about 30Pa, during low vacuum treatment, the temperature range more than 150 DEG C shows lower resistance.
It should be noted that, for the sample obtained, use spectrophotometer, measure the transmitance in wavelength 550nm, result is the visible light transmissivity that all samples shown in Fig. 6 all illustrate more than 80%.
Fig. 7 is the SEM image of the ito film obtained.The figure that the surface that this figure is the sample of 200 DEG C for heating-up temperature when using scanning electron microscope (SEM) to see drying obtains.Surface is not observed concavo-convex, can acknowledge smoothing.
As mentioned above, specify that the metal oxide film using mist to carry out film forming shows low sheet resistance.In addition known, film forming can go out have the metal oxide film of flatness, not damage light transmission.
< embodiment 2>
Aqueous dispersions containing ITO particulate is added in the 1st groove of the above-mentioned film formation device without mist collector, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produce mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.It should be noted that, use soda lime glass substrate as substrate.
In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt orthogonal with the spray direction of mist, continues the spraying of 5 minutes mists.Now, substrate substrate temperature being set as 20 DEG C to 200 DEG C is set respectively.Afterwards, at room temperature drying substrates is made.
Utilize four probe method, to obtain herein, film forming time the sheet resistance of the different metal oxide film of the temperature of substrate measure.
Fig. 8 is the figure of the sheet resistance of the different heating baking temperature that the metal oxide film obtained is shown.For the sample of substrate temperature during film forming higher than room temperature, confirm the increase of sheet resistance, i.e. the decline of electrical conductivity.In addition, for the sample by temperature more than base plate heating to 80 DEG C, for each sample, exceed the detectability of sheet resistance, therefore cannot measure.It should be noted that, the detection of this measurement is limited to 4G Ω/sq..
As mentioned above, when the temperature of substrate during film forming is below 60 DEG C, the metal oxide film with electric conductivity can be obtained.In addition, when the temperature of substrate is 25 degree close to room temperature, the highest metal oxide film of electrical conductivity can be obtained.
< comparative example 1>
Utilize spin-coating method with 500rpm by the aqueous dispersions coating containing ITO particulate on the substrate 10.Coating is at room temperature carried out.After coating, adopt the low vacuum of about 30Pa, at the temperature of 200 DEG C, carry out the heat drying of about 10 minutes.Afterwards, UV (254nm, 185nm mix) is irradiated to film surface.Then, utilize spin-coating method with 500rpm, at room temperature the aqueous dispersions containing ITO particulate is coated on substrate.After coating, adopt the low vacuum of about 30Pa, at the temperature of 200 DEG C, carry out the heat drying of about 10 minutes.It should be noted that, use soda lime glass substrate as substrate.
For the ito film obtained, use spectrophotometer, measure the transmitance in wavelength 550nm, result is the visible light transmissivity of 68%.In addition, utilize the sheet resistance of four probe method to the ito film obtained to measure, result is 800M Ω/sq..
Fig. 9 is the surface observation result based on SEM image.Compared with SEM image when carrying out film forming with Fig. 7 based on mist, rough surface when can confirm to use spin-coating method to carry out film forming.In addition, with carry out the situation of film forming based on mist compared with, sheet resistance value increases 3 number magnitude, as transparency electrode, is difficult to it and is in practical level.
In addition, utilize contact pin type film thickness gauge, carry out the mensuration of surface roughness, in embodiment 1, carrying out in the sample of 200 DEG C of heat dryings in the same manner as this comparative example, surface roughness Ra is 15nm.On the other hand, the surface roughness Ra of the film obtained in this comparative example is 80nm.
According to known above, and by making the dispersion liquid containing metal oxide microparticle be atomized, be sprayed to substrate and the film that formed is compared, the rough surface of the film formed by utilizing spin-coating method Coating dispersions, resistance value is high, and visible light transmissivity reduces.
< embodiment 3>
First, the aqueous dispersions (NanoTekSlurry:C.I.KASEI system) containing GZO particulate is prepared.The particle diameter of GZO particulate is 10 ~ 50nm, and average grain diameter is 30nm.Material and the particle diameter of GZO particulate used in other embodiments are below same with the present embodiment.In addition, the concentration of the metal oxide microparticle in dispersion liquid is 15wt.%.
Being added to by the dispersion liquid of preparation does not above-mentionedly have in the 1st groove of the film formation device of mist collector, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produces mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.It should be noted that, use soda lime glass substrate as substrate.
In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt orthogonal with the spray direction of mist, continues the spraying of 5 minutes mists.Now, not heated substrates, at room temperature sprays.
After substrate being carried out to the spraying of mist, use infrared lamp heater, carry out the heating of substrate respectively with 150 DEG C, 175 DEG C, 200 DEG C.Heating carries out about 10 minutes with the low vacuum of about 30Pa separately.
Afterwards, UV (254nm, 185nm mix) is irradiated to the surface of the GZO film of drying.Continue afterwards, as described above substrate is configured in the 2nd groove of film formation device, at room temperature continue the spraying of 5 minutes mists.Afterwards, as described above by utilizing infrared lamp heating devices heat 10 minutes, drying substrates is made.
Figure 10 illustrates the sheet resistance value of GZO film and the figure of visible light transmissivity that obtain.Known when baking temperature be 150 DEG C, 175 DEG C and 200 DEG C of arbitrary temperature, the nesa coating obtained all shows the transmitance of more than 80% in visible region.In addition, when arbitrary temperature, sheet resistance is 20M Ω/below sq..
According to known above, when metal oxide microparticle use GZO particulate, also suitable metal oxide film can be obtained.
< embodiment 4>
First, the IPA dispersion liquid (NanoTekSlurry:C.I.KASEI system) containing GZO particulate is prepared.The particle diameter of GZO and the concentration of metal oxide particle are similarly to Example 3.Being added to by the dispersion liquid of preparation does not above-mentionedly have in the 1st groove of the film formation device of mist collector, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produces mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.
After substrate being carried out to the spraying of mist, use infrared lamp heater, at the temperature of 200 DEG C, carry out the heat drying of 10 minutes with the low vacuum of about 30Pa.Afterwards, UV (254nm, 185nm mix) is irradiated to the surface of the GZO film of drying.Continue afterwards, as described above substrate is configured in the 2nd groove of film formation device, at room temperature continue the spraying of 5 minutes mists.Afterwards, as described above by utilizing infrared lamp heating devices heat 10 minutes, drying substrates is made.It should be noted that, use soda lime glass substrate as substrate.
The sheet resistance of the film obtained is 10M Ω/sq., and the transmitance in visible region is more than 80%.
Figure 11 is the SEM image of the GZO film obtained.According to the result of SEM image, form smooth film.
Figure 12 illustrates the GZO film that the obtains figure based on the analysis result of EDX.Specifically, for the GZO film obtained, the line scanning based on energy dispersion-type X-ray analysis (EnergydispersiveX-rayspectrometry:EDX) is carried out.Known according to this figure, there is significant peak in Zn and O, and the film obtained is formed with ZnO.
< embodiment 5>
Prepare the aqueous dispersions (NanoTekSlurry:C.I.KASEI system) containing GZO particulate similarly to Example 3.Being added to by the dispersion liquid of preparation does not above-mentionedly have in the 1st groove of the film formation device of mist collector, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produces mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.
In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt orthogonal with the spray direction of mist, continues the spraying of 5 minutes mists.Now, a base plate heating to 60 DEG C is sprayed, and another base plate heating to 80 DEG C is sprayed.It should be noted that, use soda lime glass substrate as substrate.
Afterwards, use infrared lamp heater, at the temperature of 200 DEG C, substrate is heated.Heating is implemented 10 minutes under the low vacuum of about 30Pa.Then, after UV (254nm, 185nm mix) is irradiated to the surface of GZO film, as described above substrate is configured in the 2nd groove, similarly heated substrates of film formation device, while continue the spraying of 5 minutes mists.Afterwards, as described above by utilizing infrared lamp heating devices heat 10 minutes, drying substrates is made.
Figure 13 is the SEM image of the GZO film obtained.When using SEM image viewing surface form, for the GZO film of the substrate formed after the heating, confirm the flatness that it loses surface.
Figure 14 is the figure of the relation of substrate temperature when film forming is shown and sheet resistance.Along with heating-up temperature during film forming rises, sheet resistance value significantly rises.It should be noted that, when heating-up temperature during film forming is 80 DEG C, sheet resistance value exceeds detectability, therefore cannot measure.
< embodiment 6>
Use spin coater, painting erosion resistant agent equably on substrate, carries out the exposure based on i ray, forms the pattern that line and gap are 100 μm.Afterwards, use dip coater using the 3M as water repellent
tMn o vec
tMeGC-1720 (Sumitomo 3M Co., Ltd. system) is coated on substrate, by peeling off anti-corrosion liquid, obtains the substrate of scolding water patterns needed for being formed with.It should be noted that, use pet substrate as substrate.
Then, similarly to Example 1, being added to by the aqueous dispersions containing ITO particulate does not above-mentionedly have in the 1st groove of the film formation device of mist collector, utilizes ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produces mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.
In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt orthogonal with the spray direction of mist, continues the spraying of 5 minutes mists.Now, substrate does not heat, and at room temperature carries out the spraying of mist.
Afterwards, use infrared lamp heater, at the temperature of 150 DEG C, substrate is heated.Heating is implemented 10 minutes under the low vacuum of about 30Pa.Then, after UV (254nm, 185nm mix) is irradiated to the film surface generated on substrate, as described above substrate is configured in the 2nd groove of film formation device, continues the spraying of 5 minutes mists.Afterwards, as described above by utilizing infrared lamp heating devices heat 10 minutes, drying substrates is made.
Figure 15 is the SEM image of the ito film of scolding on water patterns substrate.Ito film is formed in hydrophilic segment to avoid scolding the mode of water section.
According to more than, by making the dispersion liquid containing ITO particulate be atomized and spray, when forming metal oxide film thus, scold water patterns by using, can the selective metal oxide film of pattern forming expection.
< embodiment 7>
Use spin coater, painting erosion resistant agent equably on substrate, carries out the exposure based on i ray, forms the pattern that line and gap are 100 μm.Afterwards, use dip coater using the 3M as water repellent
tMn o vec
tMeGC-1720 (Sumitomo 3M Co., Ltd. system) is coated on substrate, by peeling off anti-corrosion liquid, obtains the substrate of scolding water patterns needed for being formed with.It should be noted that, use pet substrate as substrate.
Then, similarly to Example 3, prepare containing the aqueous dispersions of GZO particulate, and be added to and above-mentionedly do not have in the 1st groove of the film formation device of mist collector, utilize ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produce mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.In the 2nd groove, the state be inclined relative to horizontal to make substrate and make substrate relative to the state placement substrate of the face tilt orthogonal with the spray direction of mist, continues the spraying of 5 minutes mists.Now, substrate does not heat, and at room temperature carries out the spraying of mist.
Afterwards, use infrared lamp heater, at the temperature of 150 DEG C, substrate is heated.Heating is implemented 10 minutes under the low vacuum of about 30Pa.Then, after UV (254nm, 185nm mix) is irradiated to the film surface generated on substrate, as described above substrate is configured in the 2nd groove of film formation device, continues the spraying of 5 minutes mists.Afterwards, as described above by utilizing infrared lamp heating devices heat 10 minutes, drying substrates is made.
Figure 16 is the SEM image of the GZO film of scolding on water patterns substrate.Can confirm and scold water section different from the state of the hydrophilic segment of scolding beyond water section based on what scold water to be coated with.
< comparative example 2>
Use spin coater, painting erosion resistant agent equably on substrate, carries out the exposure based on i ray, forms the pattern that line and gap are 100 μm.Afterwards, use dip coater using the 3M as water repellent
tMn o vec
tMeGC-1720 (Sumitomo 3M Co., Ltd. system) is coated on substrate, by peeling off anti-corrosion liquid, obtains the substrate of scolding water patterns needed for being formed with.It should be noted that, use pet substrate as substrate.
Similarly to Example 1, prepare the aqueous dispersions (NanoTekSlurry:C.I.KASEI system) containing ITO particulate, be added in the 1st groove of the above-mentioned film formation device not having mist collector, utilize ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produce mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 2nd groove.
In the 2nd groove, arrange and be heated to the substrate of 60 DEG C and be heated to the substrate of 80 DEG C, for each substrate, continue the spraying of 5 minutes mists.Now, the state be inclined relative to horizontal to make substrate and make substrate relative to the state of the face tilt 45 degree orthogonal with the spray direction of mist, configures each substrate.Afterwards, infrared lamp heater is used, heated substrates at the temperature of 150 DEG C.Heating is implemented 10 minutes under the low vacuum of about 30Pa.
Figure 17 is the SEM image of the substrate being heated to 60 DEG C.Think because the evaporation rate on the substrate after the heating of the dispersion liquid containing metal oxide microparticle is exceedingly fast, be therefore attached to and scold the dispersion liquid of water section do not scolded water but there occurs evaporation.Therefore, the film forming of scolding water section also can confirm the metal oxide film of trace.
Figure 18 is the SEM image of the substrate being heated to 80 DEG C.Hydrophilic segment can be confirmed and scold water section as broad as long, having carried out the film forming of metal oxide film all sidedly.Finally cannot obtain the patterning on line.
< comparative example 3>
Use spin coater, painting erosion resistant agent equably on substrate, carries out the exposure based on i ray, forms the pattern that line and gap are 100 μm.Afterwards, use dip coater using the 3M as water repellent
tMn o vec
tMeGC-1720 (Sumitomo 3M Co., Ltd. system) is coated on substrate, by peeling off anti-corrosion liquid, obtains the substrate of scolding water patterns needed for being formed with.It should be noted that, use pet substrate as substrate.
Similarly to Example 1, prepare the aqueous dispersions (NanoTekSlurry:C.I.KASEI system) containing ITO particulate, be added in the 1st groove of the above-mentioned film formation device of mist collector, utilize ultrasonic oscillator (this polyelectron system) to apply the voltage of 2.4MHz, produce mist.By air is flowed in the 1st groove, thus the mist obtained is transported near the substrate of the 3rd groove.
Being with respect to the horizontal plane parallel in the 3rd groove, and the mode placement substrate parallel relative to the face orthogonal with the spray direction of mist, continue the spraying of 5 minutes mists.Now, not heated substrates, at room temperature sprays.
Afterwards, infrared lamp heater is used, heated substrates at the temperature of 200 DEG C.Heating is implemented 10 minutes under the low vacuum of about 30Pa.Then, after UV (254nm, 185nm mix) is irradiated to the film surface generated on substrate, as described above, substrate is configured in the 3rd groove of film formation device.It should be noted that, substrate configures in respect to the horizontal plane parallel and parallel relative to the face orthogonal with the spray direction of mist mode.For substrate, after continuing the spraying of 5 minutes mists, as described above, by utilizing infrared lamp heating devices heat 10 minutes, make drying substrates.
Figure 19 is the SEM image of the ito film obtained.Hydrophilic segment with scold water section almost as broad as long, overall for substrate, film forming goes out metal oxide film.It is believed that this is because be attached to and scold not scolded water containing the dispersion liquid of metal oxide microparticle but there occurs evaporation of water section.Finally cannot obtain the patterning seen in embodiment 6 on such line.
The result of < embodiment 2> and < comparative example 1> is investigated.Knownly be coated with compared with the situation of the dispersion liquid containing metal oxide microparticle on substrate with utilizing spin-coating method, utilize when using the film formation device of mist to carry out film forming, visible light transmissivity is high, and sheet resistance is low.In addition known, when substrate temperature during film forming is below 40 DEG C, the metal oxide film that sheet resistance is low and suitable can be obtained.
In addition, the result of < embodiment 1>, < embodiment 3> and < embodiment 4> is investigated, metal oxide microparticle is in any one situation of ITO, GZO, all can obtain suitable metal oxide film.In addition, dispersant be water, IPA any one all can obtain suitable metal oxide film.
The result of < embodiment 6>, < comparative example 2> and < comparative example 3> is investigated.Owing to scolding the formation of moisture film, use the film formation device based on mist suitably can be carried out the metal oxide film of patterning.Now, by more than base plate heating to 60 DEG C time, form metal oxide film on the whole at substrate, be difficult to form patterning.In addition known, be inclined relative to horizontal during film forming and relative to the face tilt placement substrate orthogonal with spray direction, suitably can be carried out the metal oxide film of patterning thus.
Symbol description
2: metal oxide film, 3: scold moisture film, 4: dielectric film, 5: material solution, 10: substrate, 11: resist, 21: ultrasonic oscillator, 22: air
Claims (13)
1. a manufacture method for film, wherein, it has:
Make the atomization procedure containing fine-grained dispersion liquid atomization;
Described dispersion liquid through atomization is supplied to the supply step of substrate;
Make the drying process of the described dispersion liquid drying be supplied on described substrate.
2. the manufacture method of film as claimed in claim 1, wherein, the particle diameter of described particulate contained in the dispersion liquid of atomization is below 100nm.
3. the manufacture method of film as claimed in claim 1 or 2, wherein, described substrate contains resin, has pliability.
4. the manufacture method of film as claimed any one in claims 1 to 3, wherein, described drying process carries out at the temperature of the softening point lower than described substrate.
5. the manufacture method of film as claimed in claim 4, wherein, described drying process carries out at the temperature of less than 40 DEG C more than 10 DEG C.
6. the manufacture method of the film according to any one of claim 1 to 5, wherein,
It possesses to be formed on the substrate scolds water patterns formation process by hydrophilic portion and the parent of the pattern of scolding water portion to form,
Scolding water patterns formation process to be formed with described parent to utilizing described parent scolds the substrate of water patterns to carry out described supply step.
7. the manufacture method of the film according to any one of claim 1 to 6, wherein,
After described drying process, possess the Ultraviolet radiation operation for described substrate irradiation ultraviolet radiation,
For the described substrate through described Ultraviolet radiation operation irradiation ultraviolet radiation, again carry out described supply step.
8. the manufacture method of film as claimed in claim 7, wherein,
In described supply step, described particulate contained in the described mist of supply before described Ultraviolet radiation operation is different from described particulate contained in the described mist supplied after described Ultraviolet radiation operation.
9. the manufacture method of film as claimed in claim 7 or 8, wherein,
The wavelength of below 200nm is at least comprised at the ultraviolet of described Ultraviolet radiation operation irradiation.
10. the manufacture method of film as claimed in any one of claims 1-9 wherein, wherein,
In described supply step, described substrate is inclined relative to horizontal.
The manufacture method of 11. films according to any one of claim 1 to 10, wherein,
In described supply step, described substrate is relative to the face tilt orthogonal with the described direction of the supply.
The manufacture method of 12. films according to any one of claim 1 to 11, wherein, described particulate is the metal oxide microparticle of any one containing indium, zinc, tin and titanium.
13. 1 kinds of nesa coatings, it utilizes the manufacture method of the film described in claim 12 to carry out manufacturing.
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| JP7039151B2 (en) * | 2018-06-08 | 2022-03-22 | 東芝三菱電機産業システム株式会社 | Film forming equipment |
| US20230109122A1 (en) * | 2021-07-14 | 2023-04-06 | Toyota Jidosha Kabushiki Kaisha | Method of producing electrode, and electrode production apparatus |
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| TWI764573B (en) * | 2018-01-15 | 2022-05-11 | 國立大學法人東北大學 | ITO particles, dispersion, method for producing ITO particles, method for producing dispersion, and method for producing ITO film |
| TWI784507B (en) * | 2018-01-15 | 2022-11-21 | 國立大學法人東北大學 | Manufacturing method of indium tin oxide, dispersion liquid and indium tin oxide film |
| US11692104B2 (en) | 2018-01-15 | 2023-07-04 | Tohoku University | ITO particles, dispersion, and production method of ITO film |
| US11952508B2 (en) | 2018-01-15 | 2024-04-09 | Tohoku University | ITO particles, dispersion, production method of ITO particles, production method of dispersion, and production method of ITO film |
| CN110406140A (en) * | 2019-08-07 | 2019-11-05 | 电子科技大学 | The preparation method and film of flexible electrochromic layer pattern film based on liquid-sheet disintegration self assembly |
| CN110406140B (en) * | 2019-08-07 | 2021-08-03 | 电子科技大学 | Preparation method of flexible electrochromic patterned film based on liquid film fracture self-assembly and film |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160221031A1 (en) | 2016-08-04 |
| US10328453B2 (en) | 2019-06-25 |
| JPWO2015064438A1 (en) | 2017-03-09 |
| US10702887B2 (en) | 2020-07-07 |
| US20200290082A1 (en) | 2020-09-17 |
| CN110085370A (en) | 2019-08-02 |
| WO2015064438A1 (en) | 2015-05-07 |
| JP6428636B2 (en) | 2018-11-28 |
| CN110085370B (en) | 2021-12-10 |
| US20190262858A1 (en) | 2019-08-29 |
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